CN102591137B - Ablative black film for directly making plate by flexographic plate computer and preparation method of ablative black film - Google Patents
Ablative black film for directly making plate by flexographic plate computer and preparation method of ablative black film Download PDFInfo
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Abstract
The invention relates to an ablative black film for directly making a plate by a flexographic plate computer and a preparation method of the ablative black film. The ablative black film is characterized by comprising at least one type of nano carbon black particles, one infrared laser ablative dye and two polymer adhesives, a polyether polyurethane compound modified by the first polymer adhesive polyamide and the second polymer adhesive single isocyanate, and a super dispersing agent with the structural formula of R1-X-(CH2CH2O)p-(CHCH3CH2O)q-R2. The laser ablative black film prepared by the method has high sensitivity and good film forming property and is difficult to wrinkle.
Description
Technical field
The invention belongs to laser ablation technical field of imaging, be specifically related to ablation black film that a kind of flexographic plate Computer To Plate uses and preparation method thereof.
Background technology
At present, flexographic plate is widely used in the printing of the easy distortion such as carton, flexible packaging, label or softer stock.Conventionally, the film with pattern or word is placed on the unexposed flexographic plate that contains photosensitive elastomer body, ultraviolet exposure, the place that film is transparent sees through ultraviolet light, decomposition of initiator in photosensitive elastomer body becomes free radical, causes crosslinkable monomers and reacts and solidify.Do not see through ultraviolet region cross-linking reaction can not occur, utilize the difference of their solubleness in developer solution, rinse development and obtain the relief image that contains character pattern.Plate after development is dry, goes to glue, and post-exposure, guarantees the complete polymerization of photographic layer.The plate making is fixed on the cylinder of flexible printing press, can prepare printing.
Aforementioned plate-making process need has the film of pattern or word, film is easy to be subject to the external conditions such as washing processing, dust, humidity to affect, cause disadvantage, affect the reduction of flexographic plate plate word, pattern etc., when film is attached to the plate-making of flexographic plate adherent layer simultaneously, easy bonding film and the plate-making such as refraction, the scattering disadvantage that causes light, cause the also proper mass reduction of pattern or word.
Along with the development of document processing technology before computer technology and seal, document information with pattern or word etc. can be converted into numerical information, computer control, numerical information is converted on the ablation black film that infrared laser, purple laser etc. outputs to flexographic plate, realize laser ablation imaging, no longer use film imaging, thereby eliminated the plate graph and text reduction quality reduction problem that uses film make a plate to cause.
In order to realize said process, researchist has found various solutions.US Patent No. 5719009 adopts on flexographic plate photosensitive elastomer body layer barrier layer is set, infrared laser ablation black film layer is set on barrier layer again, then use infrared laser ablation imaging, by common flexible plate making, impose the plate-making such as back of the body exposure, just exposure, solvent or buck rinsing, drying, aftertreatment again.This infrared laser ablation black film main body adopts SBS, add methyl methacrylate quarternary copolymerized resin and carbon black etc., the required laser energy of ablation layer making is thus high, easily ablation is not saturating, and the easy fold of ablation layer, the part picture and text lack of contrast of ablation and not ablation, the common flexible plate making that next impact is carried out.Jap.P. JP-A-10-119436 adopts the common heat decomposable resin such as polyester, polycarbonate, coating thickness 1-2 μ m, and its heat decomposition temperature is high, needs special laser instrument, and laser energy requirement is high, and its plate-making process and US5719009 are similar.It is matrix resin that US Patent No. 6037102 adopts water-soluble poval-polyglycol, aid in the laser heat-absorbing materials such as carbon black, realize laser ablation, but in plate-making process, be to remove the not region of laser ablation, need washing, solvent plate-making again after washing, the step that operates is many, wash version and use different developing systems, user uses complexity.US Patent No. 6521390 adopts NC Nitroncellulose, carbon black and fat group diester etc. to form ablation black film, and ablation sensitivity is high, but ablation black film while using film forming poor, when plate-making, black film easily wrinkles, and causes graph and text reduction bad.
Summary of the invention
The object of the invention is to solve the above-mentioned technical matters existing in prior art, ablation black film that a kind of flexographic plate Computer To Plate uses and preparation method thereof is provided.The easy ablation of laser ablation black film layer of the present invention's invention, ablation sensitivity is high, and good film-forming property is difficult for fold.
For achieving the above object, the technical solution used in the present invention is as follows:
The ablation black film that flexographic plate Computer To Plate of the present invention is used, is mainly made up of following component: EU compound, the structural formula of nano-particle carbon, infrared laser ablation dyestuff, the first polymer adhesive polyamide, the second polymer adhesive list isocyanide ester modification are R
1-X-(CH
2cH
2o)
p-(CHCH
3cH
2o)
q-R
2super spreading agent, in formula-X-
For-COO-,-O-,-S-,
or
; R
1, R
2, R
3, R
5independently of one another, it can be hydrogen atom, the alkyl of 1-18 carbon atom, alkyl replace or do not have the naphthenic base of 6-10 the carbon atom that alkyl replaces, the aryl or aralkyl of 6-18 carbon atom not replacing or replace, and R4 is the aryl or aralkyl that alkyl, the alkyl of 1-18 carbon atom replaces or do not have 6-18 carbon atom of the naphthenic base of 6-10 carbon atom of alkyl replacement, not replacement or replacement; P is the integer of 1-100, the integer that q is 1-150.
Mean grain size 50～the 800nm of described nano-particle carbon, accounts for the 20-50% of total solid quality at ablation black film.
Described infrared laser ablation dyestuff is the cyanine dye that contains cationic salts and anion salt structure, and it absorbs predominant wavelength at 1050-1100nm, accounts for the 0.5-10% of total solid quality at ablation black film.
The EU compound of the first polymer adhesive polyamide and the second polymer adhesive list isocyanide ester modification accounts for the 45-75% of ablation black film total solid quality altogether, and the mass ratio of the EU compound of the first polymer adhesive polyamide, the second polymer adhesive list isocyanide ester modification is between 3:1～6:1.
Described super spreading agent accounts for the 0.5-3% of ablation black film total solid quality.
The preparation method of the ablation black film that flexographic plate Computer To Plate of the present invention is used is as follows:
(1) first carbon black, infrared laser ablation dyestuff, the 60-80% of the first polymer adhesive gross mass and the 60-80% of super spreading agent gross mass are dissolved in organic mixed solvent of aromatic hydrocarbons and alcohols composition, solid material content 30-70%, first disperse 0.5-1.5 hour with high speed dispersor, and then with ball mill grinding 3-5 hour, test particle size carbon black and reach 50～800nm;
(2) the super spreading agent of the first polymer adhesive of the second polymer adhesive, surplus, surplus, surfactant and other auxiliary agents are joined in the mixed solvent of the composition such as amide-type and aromatic hydrocarbons, solid material content 30-80%, after stirring and dissolving is complete, the carbon black the dispersion liquid again first step being obtained adds, mix 3-5 hour, obtain being coated with stoste;
(3) the coating stoste of the laser ablation black film above-mentioned second step being obtained, is coated on PET or PE surface with precision coating machine, forms the thick solid cladding of 2-4 μ m, dries for 80 DEG C and within 4 hours, obtains the ablation black film that flexographic plate Computer To Plate is used.
The carbon black that in the present invention, carbon black used is preferably crossed the oxidation processes such as surperficial carboxyl, hydroxyl, can be specifically Carbon Black FW 200(Evonik), Colour Black FW 2,, SPECIAL BLACK 4 (Degussa), SPECIAL BLACK 5, SPECIAL BLACK 6, Printex U, Printex 200, at least one in JY-124.
The synergy processing of the best carboxyl of such carbon black or hydroxylation surface, carbon black after treatment more easily with the anchoring group of the hyper-dispersant of the present invention's use as-COOH ,-COO-, NR
3+, polyamine, polyvalent alcohols etc. provide adsorption activity position, form well wetting and stabilization; Simultaneously form strong hydrogen bond with the polymkeric substance such as polyamide, polyether-type, polyurethane and attract, disperse more stablely, carbon black granules is difficult for gathering and depositing.
Polymer adhesive of the present invention, the best solvent of the first polymkeric substance polyamide binder is the mixed solvent of aromatic hydrocarbons and alcohols, as easily molten in phenmethylol, methyl alcohol, ethanol, normal butyl alcohol, isopropyl alcohol, n-propanol, hexanol, benzene,toluene,xylene, ethylbenzene etc., good film-forming property, easily forms hydrogen bond with the carbon black of surface modification.If need also to add ketones solvent or esters solvent, as acetone, butanone, cyclohexanone, ethyl acetate, butyl acetate etc.
The second polymer adhesive of the present invention is the EU compound of single isocyanide ester modification preferably, be contain carboxyl by polyethers glycol and side chain glycol first with diisocyanate under catalyzer dibutyl tin laurate exists 50-80 DEG C react generation polyethers based polyurethane, then react the compound of generation with monoisocyanates at 80-90 DEG C.The compound of this structure is in the time of 130-260 DEG C, and it is free that single isocyanide ester is that heat can be decomposed, and this resin polyethers used and diisocyanate molecules amount are larger, and under heat effect, its decomposition temperature is lower.Such resin can be NP-1, NP-2, NP-31(Lekai group company) etc.Such polymer adhesive thermal degradation temperature is preferably in 300-450 DEG C, the degradation temperature of preferred, polyethers type polyurethane compound is at 350-450 DEG C. the second polymer adhesive of the present invention, best solvent is the mixed solvent of the composition such as amide-type and aromatic hydrocarbons, amide solvent can be NMF, dimethyl formamide, dimethyl acetamide etc., aromatic hydrocarbon solvent can be benzene,toluene,xylene, ethylbenzene etc., if need also can add ethyl acetate, MEK, methyl isobutyl ketone, phenmethylol etc.
Two kinds of described polymer adhesives account for the 40-80% of ablation black film total solid quality, preferably 45-75%.The mass ratio of the EU compound of the first polymkeric substance polyamide binder and the second polymkeric substance isocyanide ester modification is preferably between 3:1～6:1, and preferred mass is than between 3:1～4:1.
Laser ablation dyestuff of the present invention, adds in ablation black film, increases the density of ablation black film, can absorb the infrared laser of 900-1200nm, produce a large amount of heat, improve ablation sensitivity, stop the ultraviolet light of 300-400nm simultaneously, can not penetrate or the minimum ablation black film that penetrates.Cyanine dye that such laser ablation dyestuff can be polysubstituted phthalocyanine dye, contain cationic salts and anion salt structure, merocyanine dyes quinones, metal complex (as two thiophenols, indoaniline metal complex, azobenzene metal complex etc.), azo compound etc.The present invention preferably contains the cyanine dye of cationic salts and anion salt structure.The laser instrument predominant wavelength of using in view of current ablation black film is at 1070nm, and for mating with laser instrument better, researcher surprisingly finds that the maximum absorption wavelength of preferred infrared laser dye is in the time of 1050-1100nm, has reached the effect that reduces laser ablation energy.Such laser ablation dyestuff can be Epolight 3072 (Epolin, Inc.), Epolight 1117 (Epolin, Inc.), Epolight 1178 (Epolin, Inc.) etc.Described infrared laser ablation dyestuff, accounts for the 0.5-10% of ablation black film total solid quality, preferably the 0.5-5% of total solid quality.
The super dispersant structure formula that the present invention uses is:
R
1—X—(CH
2CH
2O)
p-(CHCH
3CH
2O)
q-R
2
Here X can be COO, O, S, R
3-N or R4 (R5)-C; R
1, R
2, R
3, R
4, R5 is independent of one another, can be hydrogen atom, the alkyl of 1-18 carbon atom, and alkyl replaces or does not have the naphthenic base of 6-10 carbon atom of alkyl replacement, the aryl or aralkyl of 6-18 the carbon atom that does not replace or replace; P is the integer of 1-100, and q is the integer of 1 to 150.The preferred COO of super spreading agent X that the present invention uses, R3-N group, the preferred H atom of R1.
The super spreading agent that the present invention is used, contains anchoring group as-COOH ,-COO-, NR
3+, polyamine, polyvalent alcohols etc. and solvation key polyethers etc., can soak black carbon surface, can directly help effective grinding, or indirectly increase carbon blacks concentration.The super spreading agent that the present invention is used, by reducing the power that attracts each other between particle, reduces system viscosity, increases the carbon black content of master grind.If needed, can use with the dispersant of other structure, also can be used in conjunction with the spreading agent of general short chain.
The present invention's super spreading agent used can grind higher carbon black concentration, make carbon black particle fragmentation rapider, prevent that the viscosity in process of lapping from raising simultaneously, spreading agent increases more tiny particle encounter stability, do not flocculate, thereby give full play to its inherent tinctorial strength.Such spreading agent can be the EFKA 4310 of Ciba company, EFKA3288, the Dispers 685 of TEGO company, Dispers 651, Dispers 662C, Dispers 710, the Solsperse 20000 of Lubrizol company, Solsperse 32500, Solsperse 24000, Solsperse 20000, Solsperse 8000, Solsperse 22000, Solsperse 5000, Solsperse 8000, Solsperse 37500, Solsperse 32000, Solsperse 27000, the Dabco T-12 of gas chemical company etc.Super spreading agent, accounts for the 0.5-5% of total solid quality, preferably accounts for the 0.5-3% of total solid quality.
In ablation black film of the present invention, also contain the auxiliary agent such as levelling agent, defoamer.If necessary, can also add UV absorbing agent, antioxidant, antiaging agent etc.
Made by the present invention ablation black film solution, by modes such as scraper, post painting, anilox roll coatings, said components is coated on to support PET or PE upper, utilizes the drying and forming-films such as hot blast, steam, infrared, microwave, for subsequent use, coating thickness 1-5 μ m, preferably figure layer thickness 2-4 μ m.In order to protect the scratch of ablation black film, the ablation black film that also coating can be obtained, is covered with film with other material such as PE or PET of 8-20 μ m, waits until for subsequent use.
The ablation black film that the present invention makes, can directly overlay on photosensitive elastomer body, if be covered with diaphragm, peels off before use diaphragm, and then overlays on photosensitive elastomer body, makes flexographic plate Computer To Plate (being called for short the soft version of CTP).
In soft edition photosensitive elastomer body layer used of CTP, at least contain a kind of thermoplastic polymeric material, at least one vinyl unsaturated compound, at least one initiating agent or initiator system, other auxiliary agents etc.
Thermoplastic polymeric material in photosensitive elastomer body layer can be multipolymer, the isoprene/cinnamic multipolymer of Butadiene/Styrene, vinyl cyanide/styrol copolymer, acrylonitrile/butadiene/styrene multipolymer, polyurethane, tygon etc., such example is as star copolymer, the acrylonitrile/butadiene/styrene multipolymer etc. of polystyrene-poly butadiene-polystyrene triblock copolymer, polystyrene-poly isoprene-polystyrene triblock copolymer, polystyrene-poly ethylene butene-polystyrene block copolymer, polystyrene-poly isoprene.
Vinyl unsaturated compound in photosensitive elastomer body layer can be that such monomer is as 2-(2 ethoxy ethoxy) ethyl propylene acid esters, isobornyl acrylate, 2-benzene oxygen ethyl propylene acid esters, tetrahydrofurfuryl alcohol acrylate, (methyl) acrylic acid-2-hydroxyl ethyl ester, acrylic acid-2-hydroxyl ethyl ester, (methyl) hydroxypropyl acrylate, butyl acrylate, (methyl) 2-ethyl hexyl acrylate, (methyl) dodecylacrylate, (methyl) octadecyl acrylate, 1,3-PD two (methyl) acrylate, BDO two (methyl) acrylate, 1,5-PD two (methyl) acrylate, 1,6-hexanediol two (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate, triethylene Glycol two (methyl) acrylate, four condensed ethandiol two (methyl) acrylate, five condensed ethandiol two (methyl) acrylate, propylene glycol diacrylate, tripropylene glycol two (methyl) acrylate, four contracting propylene glycol two (methyl) acrylate, neopentylglycol diacrylate, PDDA, phthalic acid tripropylene glycol diacrylate, ethoxylated bisphenol a diacrylate, ethoxylated trimethylolpropane triacrylate, glycerol propoxylate triacrylate, 2,2-bis-(p-hydroxybenzene)-propane two (methyl) acrylate, dihydroxy methylpropane two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, pentaerythrite two (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five acrylate, two-trimethylolpropane tetra-acrylate etc.
Initiating agent in photosensitive elastomer body layer or initiator system can be that benzophenone, rice are sneered ketone, 4-acetoxyl group-4
,-diethylamide benzophenone, benzoin ethyl ether, Alpha-hydroxy cumene ketone, Alpha-hydroxy phenylcyclohexyl ketone, 2-phenyl-2; 2-dimethoxy acetyl benzophenone, 2-tertiary butyl anthraquinone, isopropyl thioxanthone, (morpholinyl benzoyl) 1-six bases 1,1(dimethylamino) propane, benzil, benzoin etc.
In photosensitive elastomer body layer, can also add other auxiliary agents such as antioxidant, hot inhibitor, release agent, levelling agent, dyestuff.
Each component in photosensitive elastomer body layer joins in extruder in proportion; heating, mixing, exhaust etc.; at 110-150 DEG C of mixing 2-5 minute; extrude; make the sheet material of 0.5-6.35mm thickness through die head; then the heating of photosensitive elastomer body sheet material lower surface, pressurization are covered with on the support membrane that contains support and tack coat; simultaneously on the sheet material of photosensitive elastomer body layer, heating pressurization is covered with the antiseized composite membrane that contains laser ablatable layer and diaphragm again, just obtain can Computer To Plate CTP flexographic plate.
When Computer To Plate; first throw off diaphragm PET or PE; with the ablations such as the ND:YAG laser of 1064-1070nm or gasification laser ablation black film; form former bit patterns; be retained on photosensitive elastomer body layer; the part of laser ablation can see through ultraviolet light, and the part of ablation does not form mask, the penetrating of block ultraviolet.Then at plate back-exposure, form base, follow positive UV-A exposure, the part of laser ablation, ultraviolet light sees through and makes photosensitive elastomer body cross-linked polymeric, the laser not part of ablation forms mask, ultraviolet light can not see through, this part photosensitive elastomer body can not cross-linked polymeric, then in the organic solvent of zellon/normal butyl alcohol or the environmental protection developer solution that contains terpenes etc., develop, remove the laser ablation layer segment of not ablation and uncrosslinked photosensitive elastomer body, be formed with protruding pattern, dry 1.5-2 hour for 60-70 DEG C subsequently, post-exposure, go to glue, obtain the flexographic plate that can be printed on the machine.
The present invention, by add the EU compound of a kind of infrared laser ablation dyestuff, single isocyanide ester modification at ablation black film layer, reduces laser ablation energy, improves the film forming of ablation black film, is difficult for gauffer.
Embodiment
The present invention's material used is as follows:
CarbonBlack FW200 specific surface 460m2/g, primary particle diameter 13nm, surface oxidation treatment, Evonik company;
Special Black 5 specific surface area 240m2/g, primary particle diameter 20nm, surface oxidation treatment, Degussa company;
Special Black 6 specific surface area 300m2/g, primary particle diameter 17nm, surface oxidation treatment, Degussa company;
Printex 300 specific surface area 100m2/g, primary particle diameter 25nm, not oxidation place of surface, Degussa company;
Epolight 3072 laser infrared absorbing dyes, absorbing wavelength Max=1054nm, Epolin, Inc.;
Epolight 1107 laser infrared absorbing dyes, absorbing wavelength Max=1071nm, Epolin, Inc.;
Epolight 1178 laser infrared absorbing dyes, absorbing wavelength Max=1073nm, Epolin, Inc.;
Macromelt 6900 polyamides, Henkle company, softening point 128-135 DEG C, degradation temperature
350-550℃;
The copolymer resinses such as Joncryl 683 styrene and acrylic acid and propynoic acid ester class, acid number 58.1mgKOH/g,
Johnson?&?Son?Inc?;
AR-3 styrene-acrylonitrile-methacrylic acid grafting methyl propenoic acid glycidyl ether
Multipolymer, acid number 58.1mgKOH/g, Lekai group company;
The EU compound of the mono-isocyanide ester modification of NP-1, by ethylene oxide/propylene oxide block polyether glycol (PolyG55-37, mean molecular weight 3000), two hydroxymethyl propionic acid, 4,4 '-diphenyl-methane diisocyanate reaction generates end hydroxy polyether based polyurethane, then terminal hydroxy group again with the clear and electrician of methylacryoyloxyethyl isocyanates MOI(Japan) react and form, acid number 83.6 mgKOH/g, Lekai group company, decomposition temperature is less than 440 DEG C;
The EU compound of the mono-isocyanide ester modification of NP-2, by polyglycol PEG-2000, two hydroxymethyl propionic acid, 2,4-toluene diisocyanate, six methine diisocyanate reactions generate the polyethers based polyurethane that end group is hydroxyl, then terminal hydroxy group reacts and forms with methylacryoyloxyethyl isocyanates MOI again, acid number 32.1mgKOH/g, Lekai group company, decomposition temperature is less than 405 DEG C;
The super dispersing agent C iba of EFKA4310 company;
The super spreading agent TEGO of Dispers 685 company;
The super spreading agent Lubrizol of Solsperse 24000 company;
FC-4430 fluorine is surfactant B YK company;
BYK-307 silicon is surfactant B YK company.
embodiment 1
Take in table 1 39.6 grams of the Carbon Black FW2000 in embodiment 1, 15.5 grams of Macromelt 6900 polyamide, 1.0 grams of 0.5 gram of Epolight 3072 infrared laser dye and Solsperse 24000 hyper-dispersants, join 15 grams of phenmethylols, 30 grams of toluene, in the mixed solvent of 15 grams of compositions of isopropyl alcohol, first use the SWFS-400 laboratory high speed dispersor of Shanghai Solvay to disperse 1 hour, grind 3-5 hour with the SMA laboratory basket-type grinder of Shanghai Solvay again, when test particle size carbon black reaches 50-800nm, completing first step slurry grinds in advance, retain for subsequent use.
Subsequently by 0 gram of Macromelt 6900 kymene, 12.6 grams of the EU compounds of the mono-isocyanide ester modification of NP-1,0.3 gram of the super spreading agent of Dispers 685,0.7 gram, FC-4430 surfactant, joins in the mixed solvent of 8 grams of dimethyl formamides, 30 grams of toluene, 12 grams of compositions of phenmethylol, after stirring and dissolving is complete, the carbon black the dispersion liquid again first step being obtained adds, mix 3-5 hour, complete second step and mix dispersion, obtain being coated with the coating stoste of laser ablation black film.
The coating stoste of the laser ablation black film that above-mentioned second step is obtained, with being coated on pet sheet on precision coating machine
On face, dry 4 hours testing coating weight, coating density and 60 for 80 DEG C
0under rete glossiness.
Table 1
By commercially available R-284 flexographic plate (Lekai group); be cut into A3 specification; peel off diaphragm; carefully wipe adherent layer with ethanol; obtain the photosensitive elastomer body with base; then will be coated with the PET of laser ablation black film, 110 DEG C of hot pressing are on the surface of photosensitive elastomer body, the Surface Contact of laser ablation black film and photosensitive elastomer body.After room temperature preservation 72 hours, peel off the diaphragm PET of laser ablation black film, laser ablation black film exposes, from base and photosensitive elastomer body one lateral buckling 60
01 hour, angle, now laser ablation black film projection outside, is then set level plate and is kept half an hour.Above-mentioned bending in triplicate, is observed filming performance and the anti fluting of laser ablation black film.Test result is in table 2.
The filming performance of ablation black film and anti fluting, evaluation criterion is as follows:
Zero ... excellent (naked eyes be cannot see gauffer);
▲ ... better (bending curvature maximum has the fine fold vestige of 3 left and right, place 0.1-0.2mm);
× ... poor (naked eyes are seen obvious gauffer).
Peel off laser ablation black film and the photosensitive elastomer body of diaphragm and send into CDI SPARK 2120 platemaking machine (production of ESKO company); under 2540ppi; image taking speed is set as Optics10.0; the black film of ablation embodiment 1; with FAG company of Vipflex334(Switzerland) observe sharpness and the edge burr of ablation pattern, by the density that shows money or valuables one carries unintentionally of DM-500 densitometer (Screen company) mensuration laser ablation image, the density that shows money or valuables one carries unintentionally is less; mean that laser ablatable layer sensitivity is higher, institute's energy requirement is less.Test result is in table 2.
The evaluation criterion of black film ablation sensitivity:
Zero ... excellent (the clean sharp keen burr that do not have in edge, site that ablation goes out, the pattern that ablation the goes out density that shows money or valuables one carries unintentionally is less than or equal to 0.10)
▲ ... good (edge, site that ablation goes out sharper keen, burr is less, the pattern that ablation the goes out density 0.10-0.20 that shows money or valuables one carries unintentionally)
× ... poor (edge, site that ablation goes out is not sharp keen, and burr is many, and the pattern that ablation the goes out density that shows money or valuables one carries unintentionally is more than or equal to 0.20).
Embodiment 2-3 and comparative example 1-2 except starting material are pressed table 1 configuration, all the other processes with embodiment 1. evaluation results in table 2.
Table 2
| Test sequence number | Sensitivity is evaluated | Sensitivity actual measurement | Ablation black film fold is evaluated |
| Embodiment 1 | ○ | 3.27J/cm 2 | ▲ |
| Embodiment 2 | ○ | 3.16J/cm 2 | ○ |
| Embodiment 3 | ▲ | 3.34 J/cm 2 | ○ |
| Comparative example 1 | × | 3.64 J/cm 2 | × |
| Comparative example 2 | × | 4.23J/cm 2 | ▲ |
As can be seen from Table 2, the laser ablation black film layer sensitivity that the present invention makes is thus high, and good film-forming property, is difficult for fold.
Claims (6)
1. the ablation black film that flexographic plate Computer To Plate is used, is characterized in that it is mainly made up of following component: EU compound, the structural formula of nano-particle carbon, infrared laser ablation dyestuff, the first polymer adhesive polyamide, the second polymer adhesive list isocyanide ester modification are R
1-X-(CH
2cH
2o)
p-(CHCH
3cH
2o)
q-R
2spreading agent, in formula-X-is-COO-,-O-,-S-,
or
; R
1, R
2, R
3, R
5independently of one another, it can be hydrogen atom, the alkyl of 1-18 carbon atom, alkyl replace or do not have the naphthenic base of 6-10 the carbon atom that alkyl replaces, the aryl or aralkyl of 6-18 carbon atom not replacing or replace, and R4 is the aryl or aralkyl that alkyl, the alkyl of 1-18 carbon atom replaces or do not have 6-18 carbon atom of the naphthenic base of 6-10 carbon atom of alkyl replacement, not replacement or replacement; P is the integer of 1-100, the integer that q is 1-150.
2. the ablation black film that flexographic plate Computer To Plate according to claim 1 is used, is characterized in that: the mean grain size 50～800nm of described nano-particle carbon, accounts for the 20-50% of total solid quality at ablation black film.
3. the ablation black film of using according to claim 1 or flexographic plate Computer To Plate claimed in claim 2, it is characterized in that: described infrared laser ablation dyestuff is the cyanine dye that contains cationic salts and anion salt structure, it absorbs predominant wavelength at 1050-1100nm, accounts for the 0.5-10% of total solid quality at ablation black film.
4. the ablation black film that flexographic plate Computer To Plate according to claim 1 is used, it is characterized in that: the EU compound of the first polymer adhesive polyamide and the second polymer adhesive list isocyanide ester modification accounts for the 45-75% of ablation black film total solid quality altogether, and the mass ratio of the EU compound of the first polymer adhesive polyamide, the second polymer adhesive list isocyanide ester modification is between 3:1～6:1.
5. the ablation black film that flexographic plate Computer To Plate according to claim 1 is used, is characterized in that: described spreading agent accounts for the 0.5-3% of ablation black film total solid quality.
6. the preparation method of the ablation black film that flexographic plate Computer To Plate claimed in claim 1 is used, is characterized in that:
(1) first carbon black, infrared laser ablation dyestuff, the 60-80% of the first polymer adhesive gross mass and the 60-80% of spreading agent gross mass are dissolved in organic mixed solvent of aromatic hydrocarbons and alcohols composition, solid material content 30-70%, first disperse 0.5-1.5 hour with high speed dispersor, and then with ball mill grinding 3-5 hour, test carbon black mean grain size and reach 50～800nm;
(2) spreading agent of the first polymer adhesive of the second polymer adhesive, surplus, surplus, surfactant and other auxiliary agents are joined in the mixed solvent of amide-type and aromatic hydrocarbons composition, solid material content 30-80%, after stirring and dissolving is complete, the carbon black the dispersion liquid again first step being obtained adds, mix 3-5 hour, obtain being coated with stoste;
(3) the coating stoste of the laser ablation black film above-mentioned second step being obtained, is coated on PET or PE surface with precision coating machine, forms the thick solid cladding of 2-4 μ m, dries for 80 DEG C and within 4 hours, obtains the ablation black film that flexographic plate Computer To Plate is used.
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| CN102591137B true CN102591137B (en) | 2014-10-22 |
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| CN104723716A (en) * | 2013-12-19 | 2015-06-24 | 乐凯华光印刷科技有限公司 | Directly laser-made metal-based resin plate and method for making same |
| JPWO2022138713A1 (en) * | 2020-12-22 | 2022-06-30 | ||
| CN112940328A (en) * | 2021-04-20 | 2021-06-11 | 番禺南沙殷田化工有限公司 | Laser ablation black film and preparation method thereof |
| CN113280998A (en) * | 2021-05-21 | 2021-08-20 | 中国人民解放军战略支援部队航天工程大学 | Shock wave imaging system and method for laser ablation of target material |
| CN115772362B (en) * | 2022-12-20 | 2023-10-27 | 上海甚龙新材料技术有限公司 | Laser ablation composition for flexographic printing plate and preparation method thereof |
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| EP1067436A1 (en) * | 1999-07-08 | 2001-01-10 | Tokyo Ohka Kogyo Co., Ltd. | Image forming composition, image recording material comprising the same, and process of image formation |
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| WO2011008270A2 (en) * | 2009-07-14 | 2011-01-20 | Eastman Kodak Company | A system for engraving flexographic plates |
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| ATE307025T1 (en) * | 2000-03-01 | 2005-11-15 | Fuji Photo Film Co Ltd | IMAGE RECORDING MATERIAL |
| DE10061116A1 (en) * | 2000-12-07 | 2002-06-13 | Basf Drucksysteme Gmbh | Photosensitive flexographic printing element with at least two IR-ablative layers |
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| EP1067436A1 (en) * | 1999-07-08 | 2001-01-10 | Tokyo Ohka Kogyo Co., Ltd. | Image forming composition, image recording material comprising the same, and process of image formation |
| CN101040222A (en) * | 2004-10-14 | 2007-09-19 | 富林特集团德国有限公司 | Method and device for the production of photopolymerisable cylindrical jointless flexographic printing elements |
| WO2011008270A2 (en) * | 2009-07-14 | 2011-01-20 | Eastman Kodak Company | A system for engraving flexographic plates |
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